ZA200508809B - Calcium hypochlorite blended tablets - Google Patents
Calcium hypochlorite blended tablets Download PDFInfo
- Publication number
- ZA200508809B ZA200508809B ZA200508809A ZA200508809A ZA200508809B ZA 200508809 B ZA200508809 B ZA 200508809B ZA 200508809 A ZA200508809 A ZA 200508809A ZA 200508809 A ZA200508809 A ZA 200508809A ZA 200508809 B ZA200508809 B ZA 200508809B
- Authority
- ZA
- South Africa
- Prior art keywords
- tablet
- calcium hypochlorite
- weight
- magnesium sulfate
- tablets
- Prior art date
Links
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 title claims description 58
- 239000000203 mixture Substances 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 claims description 26
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 20
- 239000004571 lime Substances 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000003826 tablet Substances 0.000 description 60
- 238000012360 testing method Methods 0.000 description 33
- 239000000126 substance Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 241000238634 Libellulidae Species 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 230000009182 swimming Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- UWBXKISLLOASRQ-UHFFFAOYSA-N calcium dihypochlorite hydrate Chemical compound O.[Ca++].[O-]Cl.[O-]Cl UWBXKISLLOASRQ-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004153 Potassium bromate Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003292 diminished effect Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229940094037 potassium bromate Drugs 0.000 description 3
- 235000019396 potassium bromate Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- CAVQBDOACNULDN-NRCOEFLKSA-N (1s,2s)-2-(methylamino)-1-phenylpropan-1-ol;sulfuric acid Chemical compound OS(O)(=O)=O.CN[C@@H](C)[C@@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@@H](O)C1=CC=CC=C1 CAVQBDOACNULDN-NRCOEFLKSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 208000034699 Vitreous floaters Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- ABONIXOLZDCGIG-UHFFFAOYSA-N calcium;dihypochlorite;dihydrate Chemical compound O.O.[Ca+2].Cl[O-].Cl[O-] ABONIXOLZDCGIG-UHFFFAOYSA-N 0.000 description 1
- 239000007894 caplet Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical class [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/04—Hypochlorous acid
- C01B11/06—Hypochlorites
Description
! © 102442-201
CALCIUM HYPOCHLORITE BLENDED TABLETS
1. Field of the Invention
The present invention relates to tablets having diminished fire producing properties and is a slow dissolving product containing selected mixtures of hydrated calcium hypochlorite with magnesium sulfate heptahydrate. 2. Brief Description of Art
Hydrated calcium hypochlorite is a strong oxidizer and as such can cause a severe increase in the burning rate of combustible material with which it comes in contact. This oxidation characteristic can cause problems both in the transport and storage of the product. For example, fires involving calcium hypochlorite can be quite vigorous, particularly when combustible material is present, including the product’s packaging matenal itself (e.g., plastic, cardboard). The blends of hydrated calcium hypochlorite and magnesium sulfate heptahydrate of the invention are not classified as a “Division 5.1
Oxidizer” (i.e. they do not increase the burning rate of combustible material) as measured by an internationally recognized test standard, i.e., the United Nations Protocol: Transport of Dangerous Goods: Manual of Tests and Criteria, Section 34; Classification Procedures,
Test Methods, and Criteria relating to Oxidizing Substances of Division 5.1.
Products that are “ Division 5.1 Oxidizers” are by definition “dangerous goods” for purposes of transport. The following references have discussed this fire-causing problem and offered solutions to it.
U.S. Patent No. 3,793,216 (February 19, 1974) (assigned to Pennwalt) teaches adding water in the form of a hydrated inorganic salt to anhydrous calcium hypochlorite (less than 1% water) so that the total resulting water in the blend was from 3 to 13% resulting in a product that “provides resistance to cxothermic, self-propagating decomposition when contacted by flame, spark, or a contaminating organic substance”.
The test used in this patent to verify this property was an “ignition test”, which contacts the test sample (from 10 to 500 grams) with a lit match, or a drop of glycerin or 2- propanol. Ignition and self-propagation of burning are indicators of failure. Blends that have a delayed reaction, a less vigorous rcaction, or a localized reaction compared to anhydrous calcium hypochlorite were considered to be successful blends. However, this
! *102442-201 “ignition test” is not a demanding test. Since no fuel is present the procedure does not test the oxidizing properties, i.e., they could still increase the burning rate of combustible materials. In fact, as will be shown below, many blend products described by this
Pennwalt patent pass this ignition test but would still be classified as “Division 5.1] Oxidizers”.
U.S. Patent No. 4,201,756 (May 6, 1980), (assigned to Olin) teaches the coating of calcium hypochlorite with a plurality of layers of inorganic salts. The first layer must be comprised of salts of Periodic Table Group I alkali metal salts (sodium, potassium, lithium, rubidium, cesium or francium.) The salt must be a chloride, chlorate, nitrate, bromide, bromate, or sulfate. The first layer forms a barrier so that incompatible salts such as basic aluminum sulfate, alkalized magnesium sulfate, and sodium borates may be coated with a second layer on the pre-coated calcium hypochlorite without physical contact with the calcium hypochlorite. See column 17, lines 36 to 54. The layers of salt form a physical barricr, which resists dusting and degradation during handling, and also decreases propensity for ignition and self-sustained decomposition when contacted by a lighted match or incompatible organic materials.
There are many differences between this Olin patent and the present invention.
First, the requirement that an inert alkaline salt (such as sodium chloride) be added as a barricr between calcium hypochlorite and a material such as magnesium sulfate heptahydrate is not necessary. Second, the requirement that the final water content of the coated calcium hypochlorite be between 0.5 and 10% is actually counter-productive for reducing the oxidizing behavior of calcium hypochlorite. As such, the mechanism is different from that disclosed in this invention, which involves physically mixing the two substances so that they arc in physical contact with each other, and maintaining a water content of at least 17%.
The best indicator of the difference between the two ideas is shown using
Example XIV in the Olin patent. The example shows that calcium hypochlorite encapsulated with sodium chloride (approximately 21% by weight) prevented ignition of the material when contacted with a lighted match, i.e., it failed to undergo self-sustained decomposition. Our experiments show that physically blending 21% sodium chloride with calcium hypochlorite actually accelerates burning. As stated above, the mechanism is therefore different.
! T102442-201
In addition, calcium hypochlorite tablets have demonstrated very fast dissolving rates in water. For example, as shown in U.S. Patent Nos. 4,876,003 and 4,928,813 (both issued to Casburg and were assigned to Olin), plastic slecves were positioned around the tablet to slow down the dissolving rate of calcium hypochlorite tablets. When placed around the tablets, the tablets last longer, thus providing convenience in chlorinating swimming pools and other applications. However, such plastic sleeves afler use, must be removed from the skimmers, fecders and floaters for the swimming pools where they were used. This removal and discarding can be inconvenient to the pool owner. Alternatively, finely divided polyfluorinated polymer has been added to calcium hypochlorite tablets to cause the tablets to dissolve slower. Sec U.S. Patent Nos. 4,970,020 and 5,205,961. Other chemical blends for making calcium hypochlorite tablets are disclosed in U.S. Patent Nos. 4,145,306; 4,192,763; 4,692,335; 4,865,760; 4,961,872; 5,009,806; 5,164,109; and 5,753,602.
There is still a need in this art to produce blended calcium hypochlorite tabletted products that are (1) relatively slow dissolving product that does not require the use of a plastic sleeve or insoluble material and (2) is not classified as a Division 5.1 Oxidizer and which has enhanced safety. (i.e, diminished fire-producing properties). The present invention provides a solution to that need.
"7 102442-201
One aspect of the present invention is directed to a non-Division 5.1 Oxidizer tablet consisting essentially of a blend of hydrated calcium hypochlorite and magnesium sulfate heptahydrate, wherein the water content of the blend is at least about 17% by weight of the blend and the average dissolving rate of the tablet is less than 150 grams per day.
Another aspect of the present invention is directed to a non-Division 5.1 Oxidizer tablet consisting essentially of a blend of hydrated calcium hypochlorite and magnesium sulfate heptahydrate, wherein the water content of the blend is at least about 17% by weight of the blend; contains from about 0.1% to about 10% of lime based on the total weight of the hydrated calcium hypochlorite and magnesium sulfate heptahydrate and the average dissolving rate of the tablet is less than 150 grams per day.
The tablet of the present invention is not a Division 5.1 Oxidizer and will produce fires of dramatically diminished intensity compared to the above-noted prior art calcium hypochlorite-containing blends. Because the products of the present invention are not classified as Division 5.1 Oxidizers, they are not considered dangerous goods for purposes of transport and thus their transportation costs arc lower than the above-noted prior art blends.
Also due to the dramatically reduced intensity of any fire involving these tablets (compared to currently marketed calcium hypochlorite dihydrate tabletted products) the public good is served by the greatly enhanced safety in the storage and transportation of the product.
0 102442-201
The term “non-Division 5.1 Oxidizer composition” as used in the present specification and claims refers to any blend of calcium hypochlorite hydrate and magnesium sulfate heptahydrate that is not classificd as a UN Division 5.1 Oxidizer according to standard testing procedures now in effect.
The term “tablet” is used in the present specification and claims to cover any shape or size tablet, or other compressed shaped product made of a blend of the two critical materials. Such tablets do not cover loose granular materials such as covered by copending U.S. Patent Application Serial No. 10/271 ,375, filed on October 15, 2002, now
U.S. Patent No. 6,638,446. Such tablets may be made according to any conventional tablet-making process and/or any conventional equipment that is used for making pool sanitizer tablets.
The term “blend” is used in the present specification and claims refer to any homogeneous or near homogeneous mixture of the two critical materials. It does not . 15 include encapsulated or layered products such as covered in U.S. Patent No. 4,201,756.
The term “hydrated” as used in conjunction with calcium hypochlorite products in the present specification and claims refers to any calcium hypochlorite product that has a water content of at least 5% by weight of calcium hypochlorite product. Preferably, the compositions of the present invention consist of commercial “hydrated” (5.5% to 16% water) calcium hypochlorite, CAS number [7778-54-3] and magnesium sulfate heptahydrate, CAS number [10034-99-8]. Thesc preferred blends do not accelerate burning and are therefore non-oxidizers (as measured by the industry standard oxidizer classification test, i.e., United Nations Protocol Transport of Dangerous Goods - Oxidizing
Substances of Division 5.1).
The term “average dissolving rate” as used in the present invention, unless otherwise identified, is used to mean the static average dissolving rate of the tabletted blends of the present vention in a standing volume of water.
As stated above, the tablets of the present invention have an average dissolving rate of less than about 150 grams/day. In other words, a 300 gram tablet will take at least 2 days to dissolve completely in a standing (non-flowing) body of water. Preferably, the average dissolving rate is less than 100 grams per day for the tablets of the present invention. It should be recognized that the average dissolving rate of the tabletted blends of the present
CT 102442201 invention will generally have higher dissolving rates in flowing water conditions such as in a skimmer or a feeder in a swimming pool.
The composition preferably contains at least about 25% by weight of magnesium sulfate heptahydrate and less than about 75% by weight of hydrated calcium hypochlorite.
More preferably, these compositions contain from about 25% to about 40% magnesium sulfate heptahydrate and about 60% to about 75% by weight of hydrated calcium hypochlorite.
Also, the amount of water in the blend should be at least about 17% by weight of the total blend; more preferably, about 18% to about 24% by weight of the blend. The granular magnesium sulfate heptahydrate is physically blended with granular calcium hypochlorite to produce an essentially homogeneous granular mixture. As stated above, the blends arc not classified as UN Division 5.1 oxidizers.
The tablctted composition of the present invention may also contain small amounts of other materials as long as the presence of those materials does not cause the resulting product to be classified as a Division 5.1 Oxidizer.
One preferred material is lime (Ca(OH),) which may be included in amounts up to about 10% by weight; preferably, from about 0.1% to about 10% by weight; more preferably about 0.5% to about 3%; and most preferably, about 1% to about 2%, of the total amount of the blend of the two critical ingredients. It is believed that these blended tablets are more stable with the inclusion of lime, resulting in a long shelf life of the tablets. Also, from an operational standpoint, the inclusion of lime into the blend appears to extend the chlorine delivery time of the tablet in the aqueous environment.
The amount of water in the tabletted product may be calculated by any standard analytical method for measuring water in chemical products like these. Our preferred method is thermogravimetric analysis (TGA).
The tabletted products of the present invention may be made from granular blends of the two critical ingredients (with or without optional additives such as lime) according to any conventional tabletting process and equipment normally used for making calcium hypochlorite hydrate-containing tablets. Any suitable equipment that produces molded compacted products such as tablets, caplets or briquettes, or other known molded compacted products, using the blends of the present invention may be used. Any shape or size tablet may be used. One preferred form of tablet is shown in U.S. Patent No.
7 102442201 4,876,003. The preferred size tablet of that cylindrical shape is about 4 inches in length and about 1.8 inch in diameter. Preferred tabletting equipment includes hydraulic presses (such as Hydratron or Hydramet or Bipel hydraulic presses). Any suitable dwell times and pressures may be used in operating such hydraulic presses. Specifically, these tablets arc useful as water treatment sanitizers (e.g. in swimming pools and spas), and are especially safer to transport and store than calcium hypochlorite itself,
While not a preferred embodiment, it may be useful for some applications to place a plastic sleeve over the tabletted blends of the present invention to obtain a tabletted product that has cven longer dissolving times.
The present invention is further described in detail by means of the following
Examples and Comparisons. All parts and percentages are by weight and all temperatures are degrees Celsius unless explicitly stated otherwise.
© 102442-201 gn 353/098 Bs
The test for oxidizing substances described in Section 34 of the United Nations
Protocol was used to determine the characteristics of the various blends listed in the table below. This test is much more demanding than the glycerin “ignition” test (described earlier), requiring the presence of a substantial amount, i.e, up to 50% by weight, of a fucl (cellulose) rather than one drop of potential fuel. The detailed test method 1s described in the United Nations Recommendations on the Transport of Dangerous Goods; Manual of
Tests and Criteria; Third Revised Edition; Section 34 “Classification Procedures, Test
Methods and Criteria Relating to Oxidizing Substances of Division 5.1. In the test, the relative burning rates of the various calcium hypochlorite products are compared to those of other known oxidizers. On the basis of this test, a product can be defined as an oxidizer or a non-oxidizer. The test method states that “This test method is designed to measure the potential for a solid substance to increase the burning rate or burning intensity of a combustible substance when the two are thoroughly mixed. Tests are conducted on the substance to be evaluated mixed with dry fibrous cellulose in mixing ratios of 1:1 and 4:1, by mass, of samplc to cellulose. The burning characteristics of the mixtures are compared with the standard 3:7 mixture, by mass, of potassium bromate to cellulose. If the burning time is equal to or less than this standard mixture, the burning times should be compared with those from packing group I or II reference standards, 3:2 and 2:3, by mass of potassium bromate to cellulose respectively.”
By definition, a substance that is not Division 5.1 Oxidizer (1.e., not an oxidizing substance) is any substance which, in both the 4:1 and 1:1 sample-to-cellulose ratio (by mass) tested, does not ignite and burn, or exhibits mean burning times greater than that of a 3:7 mixture (by mass) of potassium bromate and cellulose.
The following blends of both hydrated and anhydrous calcium hypochlorite with other materials were evaluated using the test method discussed above.
CT 10244220)
Table 1. Testing results of various calcium hypochlorite (anhydrous and hydrated) blends using the UN Division 3.1 oxidizer classification test.
Blend Components Ratio %H,0in | 5.1 blend Oxidizer
Blends with “anhydrous” Ca(0Cl), 1 Ca(OCl),/CaS0,42H,0 80/20 5.0 Yes
Ca(OCl)2/Na,B404-5H,0 80/20 Yes
Ca(OC1),/Na;PO,+12H,0 85/15 Yes 4 Ca(OCl1)2/MgS047H,0 90/10 Yes
Ca(OCl)/MgS0O,*7H,0 75/25 13.5 Yes 6 Ca(OCl),/MgS047H,0 70/30 16.0 Yes
Blends with “hydrated” Ca(0Cl),
Ca(OCl1),*2H,0/CaS04-2H,0 80/20 Yes 5 | CaOCh ALONmBO SHO [020 [110 [Yer
Ca(OChy Z,OMNaPO, 12,0 [55715
CaO) 2H,0MgSOTH0 | 90710 1 | Ca(OC): 2,0MsSOr TO | 7575
CaO: 2H,0MgS0TH,0 | 70730 5 Note that the tests were run both with anhydrous (less than 1% water) and hydrated (6% water) calcium hypochlorite, although it should be noted that hydrated calcium hypochlorite did not exist on a commercial basis when the carlier Pennwalt work was done.
The tests show that the first four blends in the table (Examples 1-4), while they arc within the scope of the Pennwalt patent, do not pass the UN Division 5.1 Oxidizer test.
All are classified as oxidizers by that test.
© 102442-20
The only blends that pass the UN Division 5.1 Oxidizer (1.€., are not oxidizers) are the 75/25 and 70/30 hydrated cal hypo/MgS0,4+7H,0 blends (Examples 11 and 12). Note that neither the 75/25 nor the 70/30 anhydrous calcium hypochlorite/MgSO4+7H,0 blends (Examples 5 and 6) pass thc UN Division 5.1 Oxidizer test. Both the 75/25 and 70/30 hydrated cal hypo/ MgS0,*7H,0 blends are outside of the scope of the Pennwalt patent for at least two reasons. First, as stated carlier, hydrated calcium hypochlorite did not exist commercially at that time, and, sccond, the products both contain substantially more than 13% water cited in the Pennwalt patent.
Further testing also showed that the 70/30 blend of hydrated calcium hypochlorite and magnesium sulfate heptahydrate did not accelerate the burning of the product in 5-1b. plastic bottles. The bottles containing the blends of Examples 11 and 12, when artificially set on fire using kerosenc and a torch burned slowly, showing a burn rate similar to the empty plastic packages themselves. Conversely, calcium hypochlorite hydrate alone in the same quantity and packaging, burned quite vigorously.
Continuous Flow Tablet Dissolving Test
Six formulations noted below in Table 2 were prepared by first homogenously blending the listed ingredients together for cach formulation and then preparing six batches of tablets of such blends that weighed 285 grams each. These tablets were produced on either Bipel or Hydratron hydraulic tabletting machine into a shape similar to the cylindrical tablets shown in U.S. Patent No. 4,876,003 (Casberg et al.). The Bipel press was a 3-tablet, 70 ton Split Preformer Bipel Hydraulic Press. The batches made with it had dwell times between 2.4 and 3.0 seconds and the pressures were 2800-3100 psig.
The Hydratron Press was a 30 ton, Single Tablet, Hydratron Hydraulic Press. The batches made with it were run at 0.6 sccond dwell and a pressure of 2100-2200 psig.
© 102442-201
Table 2
Calcium Hypochlorite Hydrate/Magnesium Sulfate Heptahydrate/Lime
Formulations
Formulation | Ca(OCI);.2H,0 MgSO47TH,0 | Ca(OH), i 0 3 70 28.5 1.5 : 70 29 55
Co 983 0 *Formulation had a plastic sleeve around the tablet as shown in U.S. Patent No. 4,876,003.
These tablets of such formulation were then placed in separate skimmers in a swimming pool. The flow rate of water through the skimmers was 30 gallons per minute.
The size basket of the skimmer was 6.5 inches. The test was run with the water flow on for 12 continuous hours and then off for 12 continuous hours for each day. During the off period, the tablets were submerged under water in the skimmer. These tablets were removed from the skimmers at periodic time intervals and weighed. The approximate average dissolving rates of each formulation over a 2 to 6-day test period are shown below in Table 3.
Table 3
Average Dissolving
Formulation Rates (grams/day)
~ 2.13/08809
Static Dissolving Tests
Four formulations noted below in Table 4 were prepared by first homogenously blending the listed ingredients together for each formulation and then preparing tablets of such blends. Each tablet weighed 285 grams. These tablets were produced on a hydraulic tabletting machine all from batches about 200 pounds cach into a shape similar to the cylindrical tablets shown in U.S. Patent No 4,876,003 (Casberg et al.). These tablets were all produced on the 30 ton, Single Tablet, Hydratron Hydraulic Press. The pressing pressure for all batches was 2500 to 2800 psig with a 0.2 second dwell.
Table 4
MESO. 7H0
AS ES ES NS XS
2 TTm% sen
Ee SS — * —— — 4] 70% | 2% 3%
Each pre-weighted tablet was placed in a basket in 3 liters of water. There was no stirring of the water for 5 ¥; hours. The tablet was removed and re-weighed, then the water was mixed vigorously for 30 minutes before being analyzed for Cl, content. The water was allowed to settle and the tablets were placed back in their baskets until next time for measurement. The mixing and analyzing procedures were repeated. The results of these measurements are shown in Table 5 below.
* LJ . as 2 sl Sa
Cae] i 3 Sith wil ov 28 mE olen la - i Ee a HE o0 bE Be & aC gl ZS] IQISIZIZ EE] 12022] enn © 8 0 SE go) Cle —lelooE | —jo|o|o
SU ats 2 fe we _ ry EY SN Sn
SE | pe : g ° & 2% | d 2, a. = a) ast Y gg ke 4 2: >) Nd ere 3 Ea — 2 gE ZIQISkA [222 0 EA EES 0 oy ® oa Eo ciel—. Sd I SIO —|—
Lo. a Td HS
SO fr i 5 bi 25 oh id wl ER
SIT i 2 an
Lk i i SN ha La ef —_ Bu rl Sa Ss go .2 be a ed Fig oS w es Ri Es Ld aS HE (o|o|o|olE i fel rt - EE © 00 || D Fn QIN | On fd; 00 i
O28 ESN EIFICE S| nese : a 2 SISISI8 [=] 5 i ol © 3 S Hi Zlolg iS] — oy . Gel Ol Mio op @ Sis Nel ha EO NE pA id | — joo [00] a > ie —| == NTA Lo A a INTE A =a Fu oe Ei Le ~ UE wa LE es
EH ho i To 4 Fs 5 us
HE i oe i o iy a a 8 OD, 3 = fo — 5 BY Tum 4 0.
Os Ploln|a|o on [2 0000] on [0 BB] o |< [ooo [13] o wn 5 fan 1110 1100 Jogi AR ARIST FE R= -E R EN Regs Po La PA PE EN = (2 ey LS = ie o [3 © = i >: Tn xl ash ™ hand x 3 fos fo — a i 2 = =! 0: Io] Er =. p= +3 aD - DO - . ad Bs : j=4 = = a NH) N iS.
EO Si2i222 1282212 122g 20 2 eo lE elo cleo oO © Ly HlQecioirFo|olo|o|oiic|s| S| alls ~ [A aN NEE NAN Np (NNN NH NNR &
RAE ey LE UE
Foye a Li aE [Eh A i 45 ie = i! «loo Ee El ’ Ed + wv he wy [ON Fs SE —_ 0 4 HBR =| QR en | 0B oe ol ZI
S 9 S| =H ZS sles |S SEEN A E=1 I= hd FO INE
Gi Se Tae lool SN lols |R [2 2 5 ONAN Es NON 7 a & wa < SINS I) tak a oi BE
Kis bes Sl Ec — reas ri Soh = SND = t “Halen en a Jove) Es 50 . Li = NS Blanca oe IRIRIR|B |e |S IRIe|o ‘Q oe selon J glo |o|—= aE H os < os |S 2 og eS = SURAT OQ FIRS TSS a0 RI QEHRIR|Z Ro ol 5 A DRT Aa I 31 Et Kt het Rv RT EY PAT BE rs add Gail HE gis i Fa = [7 ie 4 led Fn a 8 = ol Vltion|e : |< oy “ ty
Si : REN ! 00 JN ol [nn = OQ be ol ae be : or Mr {oo|eN = HITT ETT Ra To TS Se Id NIST A
Pr SE] Gh Ey
Tr Bi 2 al a 5 NR SE
El pat iE por =F Seg rad —_ g i ol i Bh
S = ss ry oo o s FR ha i, Ed
AN = £228 ow Se ee po 3 £ ik 3 3k 3 Ep ~ f. Lan i 3 Ea iE
S S 5 i Git 0
© 102442205
The average dissolving rate of each tablet is shown below: ew 2 74
LL 4 58
AVAILABLE CHLORINE LOSS WITH AND WITHOUT LIME bh) Five types of 20 gram samples were placed in sealed glass vials and were heated for either 10 or 20 days in a Fisher Isotemp 200 Series Model 230G oven that was preheated at 45°C.
These five types of samples were as follows: (1) Control -- Standard hydrated calcium hypochlorite granules (commercially available from Arch Chemicals as HtH® Poolife® Active Cleaning hydrated calcium hypochlorite granules). (2) Regranulated Duration brand hydrated calcium hypochlorite tablets having no lime included therein. Duration tablets are available from Arch Chemicals, Inc. Regranulation of these tables was effected manually by use of a mortar and pestle. (3) Regranulated Duration brand hydrated calcium hypochlorite tables having 1.5% by weight lime (Ca(OH),) incorporated therein. Duration tablets are available from Arch
Chemicals, Inc. Regranulation of these tablets was effected manually by use of a mortar and pestle. 4) Regranulated hydrated calcium hypochlorite tablets that contained 70% by weight hydrated calcium hypochlorite and 30% by weight magnesium sulfate heptahydrate.
Regranulation of these tables was effected manually by use of a mortar and pestle. 5) Regranulated hydrated calcium hypochlorite tables that contained 70% by weight hydrated calcium hypochlorite, 29% by weight magnesium sulfate heptahydrate and 1% by weight lime (Ca(OH),) incorporated therein. Regranulation was effected manually by a mortar and pestle.
The available chlorine in the sample was measured before and after each run. This available chlorine analysis was conducted by titration with standardized sodjum thiosulfate to a starch iodide endpoint. These 10 or 20 day oven tests simulate the loss of available chorine in packaged products under either 1 year or 2 years of normal storage conditions.
The amount of loss of available chorine for each sample run during the 20 day oven test are shown in Table 6.
The amount of loss of available chlorine for each sample run during the 10 day oven test arc shown in Table 7.
TABLE 6
Loss of Available Chlorine
Total summary for 20 Days in Oven - 2 year Field Simulation
Cal Hypo Tablets Tablets
Alone No Lime 1.5% Lime
ECL
En —
Bl —
BC FO 0 BL
MC I NJ LZ BY
BEEN I EE NC LL
: © 102442201
TABLE 7
Loss of Available Chlorine
Total summary for 10 Days in Oven - 1 year Field Simulation
Granular Duration Duration Calhypo/Mg(SO,),- 7TH,0
Cal Hypo Tablets Tablets
Alone No Lime 1.5% Lime | No Lime 1.0% Lime ~ Run#l 2.95 4.14 3.52 2.06
EL I
I EE REL
CL es
BC CL EN I I
These results indicate that the addition of lime to the hydrated calcium > hypochlorite/magnesium sulfate heptahydrate blended product of the present invention clearly increases its available chlorine stability, resulting in longer shelf life.
While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications, and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications and variations that fall within the spirit and broad scope of the appended claims. All patent applications, patents and other publications cited herein are incorporated by reference in their entirety.
Claims (12)
1. A non-Division 5.1 Oxidizer tablet consisting essentially of a blend of hydrated calcium hypochlorite with magnesium sulfate heptahydrate, wherein the blend contains at least about 17% by weight of water based on the total weight of the blend and the average dissolving rate of the tablet is less than 150 grams per day.
2. The tablet of claim 1 wherein the composition contains at least 25% by weight of magnesium sulfate heptahydrate and less than about 75% by weight of hydrated calcium hypochlorite.
3. The tablet of claim 1 wherein the composition contains about 25% to about 40% by weight of magnesium sulfate heptahydrate and 60% to 75% of hydrated calcium hypochlorite.
4. The tablet of claim 1 wherein the amount of water in the composition is from 18% to 24% by weight of the composition.
5. The tablet of claim 1 wherein the average dissolving rate is less than about 100 grams per day.
6. A non-Division 5.1 Oxidizer tablet consisting essentially of a blend of hydrated calcium hypochlorite with magnesium sulfate heptahydrate, wherein the blend contains at least about 17% by weight of water based on the total weight of the blend; contains from
0.1% to 10% of lime based on the total weight of the hydrated calcium hypochlorate and magnesium sulfate heptahydrate and the average dissolving rate of the tablet is less than 150 grams per day.
7. The tablet of claim 6 wherein the composition contains at least 25% by weight of magnesium sulfate heptahydrate and less than about 75% by weight of hydrated calcium hypochlorite. AMENDED SHEET f
8. The tablet of claim 6 wherein the composition contains about 25% to about 40% by weight of magnesium sulfate heptahydrate and 60% to 75% of hydrated calcium hypochlorite.
09. The tablet of claim 6 wherein the amount of water in the composition is from about 18% to about 24% by weight of the composition.
10. The tablet of claim 6 wherein the tablet contains from about 0.5% to about 3% by weight of lime, said percentage based on the combined weight of the hydrated calcium hypochlorite and magnesium sulfate heptahydrate.
11. The tablet of claim 6 wherein the tablet contains 1% to 2% by weight of lime, said percentage based on the combined weight of the hydrated weight of the hydrated calcium hypochlorite and magnesium sulfate heptahydrate.
12. The tablet of claim 6 wherein the average dissolving rate is less than about 100 grams per day. AMENDED SHEET
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/405,388 US6984398B2 (en) | 2003-04-02 | 2003-04-02 | Calcium hypochlorite blended tablets |
Publications (1)
Publication Number | Publication Date |
---|---|
ZA200508809B true ZA200508809B (en) | 2006-07-26 |
Family
ID=33097084
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200508809A ZA200508809B (en) | 2003-04-02 | 2005-10-31 | Calcium hypochlorite blended tablets |
Country Status (11)
Country | Link |
---|---|
US (3) | US6984398B2 (en) |
CN (1) | CN100522136C (en) |
AR (1) | AR043830A1 (en) |
AT (1) | ATE484484T1 (en) |
DE (1) | DE602004029526D1 (en) |
EC (1) | ECSP056099A (en) |
ES (1) | ES2354042T3 (en) |
PE (1) | PE20050210A1 (en) |
SA (1) | SA04250062B1 (en) |
TW (1) | TWI340731B (en) |
ZA (1) | ZA200508809B (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4601608B2 (en) * | 2003-04-02 | 2010-12-22 | アーチ ケミカルズ,インコーポレイテッド | Tablets blended with calcium hypochlorite |
US6984398B2 (en) * | 2003-04-02 | 2006-01-10 | Arch Chemicals, Inc. | Calcium hypochlorite blended tablets |
US7045077B2 (en) * | 2004-06-18 | 2006-05-16 | Biolab, Inc. | Calcium hypochlorite compositions |
US7820198B2 (en) * | 2004-10-19 | 2010-10-26 | Arch Chemicals, Inc. | Pool chemical tablet |
US8252200B2 (en) * | 2005-12-01 | 2012-08-28 | Arch Chemicals, Inc. | Coated calcium hypochlorite composition |
US7431863B2 (en) * | 2006-03-08 | 2008-10-07 | Ppg Industries Ohio, Inc. | Calcium hypochlorite composition |
US7758709B2 (en) | 2006-06-21 | 2010-07-20 | Autoliv Asp, Inc. | Monolithic gas generant grains |
US7625496B2 (en) * | 2006-11-03 | 2009-12-01 | Chemtura Corporation | Solid composition for treating water |
US9193639B2 (en) | 2007-03-27 | 2015-11-24 | Autoliv Asp, Inc. | Methods of manufacturing monolithic generant grains |
US8372291B2 (en) * | 2007-04-20 | 2013-02-12 | Arch Chemicals, Inc. | Calcium hypochlorite compositions comprising zinc salts and lime |
US7927510B2 (en) * | 2007-04-20 | 2011-04-19 | Arch Chemicals, Inc. | Calcium hypochlorite compositions comprising zinc salts and lime |
US8057611B2 (en) * | 2007-08-13 | 2011-11-15 | Autoliv Asp, Inc. | Multi-composition pyrotechnic grain |
US8815029B2 (en) * | 2008-04-10 | 2014-08-26 | Autoliv Asp, Inc. | High performance gas generating compositions |
US8808476B2 (en) * | 2008-11-12 | 2014-08-19 | Autoliv Asp, Inc. | Gas generating compositions having glass fibers |
US8361945B2 (en) * | 2008-12-09 | 2013-01-29 | The Clorox Company | Solid-layered bleach compositions and methods of use |
US8287755B2 (en) | 2008-12-09 | 2012-10-16 | The Clorox Company | Solid-layered bleach compositions |
US8361942B2 (en) * | 2008-12-09 | 2013-01-29 | The Clorox Company | Hypochlorite denture compositions and methods of use |
US8361944B2 (en) * | 2008-12-09 | 2013-01-29 | The Clorox Company | Solid-layered bleach compositions and methods of use |
US8920743B2 (en) | 2011-04-06 | 2014-12-30 | The Clorox Company | Faucet mountable water conditioning devices |
US9051223B2 (en) | 2013-03-15 | 2015-06-09 | Autoliv Asp, Inc. | Generant grain assembly formed of multiple symmetric pieces |
GB2532070B (en) | 2014-11-07 | 2018-05-09 | Xanadox Tech Limited | Improvements relating to hypochlorous acid solutions |
MX2017014578A (en) | 2015-05-14 | 2018-03-09 | Arch Chem Inc | Slow dissolving hypochlorite containing tablet. |
MX2019008599A (en) * | 2017-01-20 | 2019-09-09 | Innovative Water Care Llc | Low reactivity calcium hypochlorite shaped article. |
Family Cites Families (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1277135A (en) | 1968-09-27 | 1972-06-07 | Unilever Ltd | Detergent compositions |
GB1317183A (en) | 1969-05-30 | 1973-05-16 | Unilever Ltd | Cleansing compositions |
FR2063713A5 (en) * | 1969-10-28 | 1971-07-09 | Instr Controle Ana | |
US3793216A (en) | 1971-12-06 | 1974-02-19 | Pennwalt Corp | Calcium hypochlorite composition |
US4174411A (en) * | 1972-07-31 | 1979-11-13 | Olin Corporation | Granular calcium hypochlorite coated with an inorganic salt by spray graining |
US4201756A (en) * | 1972-07-31 | 1980-05-06 | Olin Corporation | Granular calcium hypochlorite coated with an inorganic salt |
US4118524A (en) | 1972-07-31 | 1978-10-03 | Olin Corporation | Granular calcium hypochlorite by spray graining |
US4289640A (en) * | 1974-01-21 | 1981-09-15 | Colgate-Palmolive Company | Cleaning compositions |
US4051056A (en) | 1974-09-09 | 1977-09-27 | The Procter & Gamble Company | Abrasive scouring compositions |
US4048351A (en) | 1974-11-06 | 1977-09-13 | Olin Corporation | Granular calcium hypochlorite coated with a low melting inorganic salt by spray graining |
US3969546A (en) | 1974-11-06 | 1976-07-13 | Olin Corporation | Process for preparing granular calcium hypochlorite in a fluidized bed |
US4146676A (en) * | 1975-03-12 | 1979-03-27 | Olin Corporation | Granular calcium hypochlorite coated with a low melting inorganic salt by spray graining |
US4005028A (en) | 1975-04-22 | 1977-01-25 | The Procter & Gamble Company | Organosilane-containing detergent composition |
JPS593924B2 (en) | 1976-03-25 | 1984-01-26 | 日本曹達株式会社 | Molded calcium hypochlorite composition |
US4071605A (en) * | 1977-01-31 | 1978-01-31 | Olin Corporation | Process for the production of dibasic magnesium hypochlorite |
ZA77938B (en) * | 1977-02-16 | 1978-08-30 | P Buchan | Chlorine tablet and the preparation thereof |
US4216027A (en) * | 1978-04-18 | 1980-08-05 | The Procter & Gamble Company | Method and apparatus for cleansing and disinfecting a flushing toilet |
US4208756A (en) * | 1978-07-31 | 1980-06-24 | Smith Samuel C | Chimney cleaner |
AU536179B2 (en) * | 1979-05-29 | 1984-04-19 | Toyo Soda Manufacturing Co. Ltd. | Calcium hypochlorite |
US4380533A (en) * | 1980-03-12 | 1983-04-19 | Olin Corporation | Process for the production of dibasic magnesium hypochlorite |
US4668475A (en) * | 1982-04-02 | 1987-05-26 | Twinoak Products, Inc. | Cleaning and disinfecting method and article of manufacture including color display |
US4539179A (en) * | 1982-04-02 | 1985-09-03 | Twinoak Products, Inc. | Method for cleansing and disinfecting toilet tanks and bowls |
US4931207A (en) * | 1984-01-27 | 1990-06-05 | The Clorox Company | Bleaching and bluing composition and method |
US4615794A (en) * | 1984-08-20 | 1986-10-07 | Belanger Roger L | Method of removing radioactive waste from oil |
GB8515181D0 (en) * | 1985-06-14 | 1985-07-17 | Jeyes Group Ltd | Lavatory cleansing compositions |
US4692335A (en) * | 1985-09-03 | 1987-09-08 | Ppg Industries, Inc. | Calcium hypochlorite tablet |
JPS63130508A (en) * | 1986-11-18 | 1988-06-02 | Tosoh Corp | Calcium hypochlorite composition and production thereof |
US4961872A (en) * | 1987-10-26 | 1990-10-09 | The Drackett Company | Calcium hypochlorite tablets |
US4865760A (en) * | 1988-04-06 | 1989-09-12 | Ppg Industries, Inc. | Calcium hypochlorite composition |
US5009806A (en) * | 1988-04-06 | 1991-04-23 | Ppg Industries, Inc. | Calcium hypochlorite article |
US4970020A (en) * | 1988-04-06 | 1990-11-13 | Ppg Industries, Inc. | Calcium hypochlorite composition |
US4876003A (en) * | 1988-05-09 | 1989-10-24 | Olin Corporation | Encased pool chemical tablet with domed ends |
US4928813A (en) * | 1989-06-02 | 1990-05-29 | Olin Corporation | Encased pool chemical capsule with extended ends and method of making the same |
US5164109A (en) * | 1990-05-31 | 1992-11-17 | Olin Corporation | Algicidally enhanced calcium hypochlorite compositions |
US5205961A (en) * | 1991-04-18 | 1993-04-27 | Ppg Industries, Inc. | Granular calcium hypochlorite treatment process |
FR2715590B1 (en) * | 1994-02-01 | 1996-04-12 | Rhone Poulenc Chimie | Process for purifying a medium containing organic waste. |
US5763302A (en) * | 1995-06-07 | 1998-06-09 | Lsi Logic Corporation | Self-aligned twin well process |
US5707534A (en) * | 1995-07-10 | 1998-01-13 | Buckman Laboratories International, Inc. | Use of tabletized ionene polymers in water treatment |
US5753602A (en) * | 1995-12-18 | 1998-05-19 | The Block Drug Company | Chlorine cleanser tabletting process and product |
US5888528A (en) * | 1997-05-19 | 1999-03-30 | Bernard Technologies, Inc. | Sustained release biocidal powders |
US5756440A (en) * | 1997-05-27 | 1998-05-26 | The Clorox Company | Solid, water-degradable disinfectant and cleanser composition, and associated methods of manufacture and use |
US6638446B1 (en) | 2002-10-15 | 2003-10-28 | Arch Chemicals, Inc. | Lower reactivity blends of calcium hypochlorite and magnesium sulfate |
US6984398B2 (en) * | 2003-04-02 | 2006-01-10 | Arch Chemicals, Inc. | Calcium hypochlorite blended tablets |
US7045077B2 (en) * | 2004-06-18 | 2006-05-16 | Biolab, Inc. | Calcium hypochlorite compositions |
-
2003
- 2003-04-02 US US10/405,388 patent/US6984398B2/en not_active Expired - Lifetime
-
2004
- 2004-02-20 US US10/783,210 patent/US6969527B2/en not_active Expired - Lifetime
- 2004-03-15 CN CNB2004800087048A patent/CN100522136C/en not_active Expired - Fee Related
- 2004-03-26 DE DE602004029526T patent/DE602004029526D1/en not_active Expired - Lifetime
- 2004-03-26 ES ES04251781T patent/ES2354042T3/en not_active Expired - Lifetime
- 2004-03-26 AT AT04251781T patent/ATE484484T1/en not_active IP Right Cessation
- 2004-03-31 SA SA04250062A patent/SA04250062B1/en unknown
- 2004-03-31 TW TW093108979A patent/TWI340731B/en not_active IP Right Cessation
- 2004-03-31 PE PE2004000336A patent/PE20050210A1/en active IP Right Grant
- 2004-04-01 AR ARP040101110A patent/AR043830A1/en active IP Right Grant
-
2005
- 2005-10-13 EC EC2005006099A patent/ECSP056099A/en unknown
- 2005-10-31 ZA ZA200508809A patent/ZA200508809B/en unknown
- 2005-12-21 US US11/314,512 patent/US20060093669A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20060093669A1 (en) | 2006-05-04 |
ES2354042T3 (en) | 2011-03-09 |
US20040197395A1 (en) | 2004-10-07 |
US6984398B2 (en) | 2006-01-10 |
US6969527B2 (en) | 2005-11-29 |
TW200503946A (en) | 2005-02-01 |
AR043830A1 (en) | 2005-08-17 |
CN1767813A (en) | 2006-05-03 |
PE20050210A1 (en) | 2005-03-28 |
TWI340731B (en) | 2011-04-21 |
DE602004029526D1 (en) | 2010-11-25 |
US20040214738A1 (en) | 2004-10-28 |
SA04250062B1 (en) | 2008-01-08 |
CN100522136C (en) | 2009-08-05 |
ECSP056099A (en) | 2006-03-01 |
ATE484484T1 (en) | 2010-10-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
ZA200508809B (en) | Calcium hypochlorite blended tablets | |
US20060110453A1 (en) | Calcium hypochlorite blended tablets | |
US7695639B2 (en) | Calcium hypochlorite compositions | |
KR101409142B1 (en) | Stabilized composition for producing chlorine dioxide | |
US7182883B2 (en) | Massive bodies containing free halogen source for producing highly converted solutions of chlorine dioxide | |
CA2631169C (en) | Coated calcium hypochlorite composition | |
EP3068222B1 (en) | Disinfectant composition | |
US6638446B1 (en) | Lower reactivity blends of calcium hypochlorite and magnesium sulfate | |
US7465412B2 (en) | Calcium hypochlorite composition | |
CA3050688C (en) | Low reactivity calcium hypochlorite shaped article | |
JP2006522805A (en) | Solid biocide | |
US20230242425A1 (en) | Novel slow dissolve water treatment compositions | |
US20100317558A1 (en) | Use of a blend containing percarbonate for detergents and dishwashing formulations | |
US20110052724A1 (en) | Calcium hypochlorite compositions | |
NO144150B (en) | Bleach, Sterilization, Disinfectant and Detergent Mixtures |